Kinetic Fractionation of Non-Traditional Stable Isotopes by Diffusion and Crystal Growth Reactions

Natural variations in the isotopic composition of some 50 chemical elements are now being used in geochemistry for studying transport processes, estimating temperature, reconstructing ocean chemistry, identifying biological signatures, and classifying planets and meteorites. Within the past decade, there has been growing interest in measuring isotopic variations in a wider variety of elements, and improved techniques make it possible to measure very small effects. Many of the observations have raised questions concerning when and where the attainment of equilibrium is a valid assumption. In situations where the distribution of isotopes within and among phases is not representative of the equilibrium distribution, the isotopic compositions can be used to access information on mechanisms of chemical reactions and rates of geological processes. In a general sense, the fractionation of stable isotopes between any two phases, or between any two compounds within a phase, can be ascribed to some combination of the mass dependence of thermodynamic (equilibrium) partition coefficients, the mass dependence of diffusion coefficients, and the mass dependence of reaction rate constants. Many documentations of kinetic isotope effects (KIEs), and their practical applications, are described in this volume and are therefore not reviewed here. Instead, the focus of this chapter is on the measurement and interpretation of mass dependent diffusivities and reactivities, and how these parameters are implemented in models of crystal growth within a fluid phase. There are, of course, processes aside from crystal growth that give rise to KIEs among non-traditional isotopes, such as evaporation (Young et al. 2002; Knight et al. 2009; Richter et al. 2009a), vapor exsolution (Aubaud et al. 2004), thermal diffusion (Richter et al. 2009a, 2014b; Huang et al. 2010; Dominguez et al. 2011), mineral dissolution (e.g., Brantley et al. 2004; Wall et al. 2011; Pearce et al. 2012 …